WO2012102153A1 - Procédé de production d'une fibre cellulosique hydrophilisée et procédé de réduction d'une fibre cellulosique oxydée - Google Patents

Procédé de production d'une fibre cellulosique hydrophilisée et procédé de réduction d'une fibre cellulosique oxydée Download PDF

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WO2012102153A1
WO2012102153A1 PCT/JP2012/050992 JP2012050992W WO2012102153A1 WO 2012102153 A1 WO2012102153 A1 WO 2012102153A1 JP 2012050992 W JP2012050992 W JP 2012050992W WO 2012102153 A1 WO2012102153 A1 WO 2012102153A1
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cellulose fiber
producing
oxidized cellulose
treatment
reaction solution
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PCT/JP2012/050992
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English (en)
Japanese (ja)
Inventor
明 磯貝
千晶 田中
美也 由井
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グンゼ株式会社
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Priority to EP12739540.8A priority Critical patent/EP2669425A1/fr
Priority to CN201280005803.5A priority patent/CN103328715B/zh
Priority to JP2012554743A priority patent/JP5774031B2/ja
Priority to US13/993,448 priority patent/US9296829B2/en
Priority to KR1020137022050A priority patent/KR20140003559A/ko
Publication of WO2012102153A1 publication Critical patent/WO2012102153A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/34—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxygen, ozone or ozonides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic

Definitions

  • the present invention relates to a method for producing hydrophilic cellulose fibers and a method for reducing oxidized cellulose fibers, and more specifically, a method for producing hydrophilic cellulose fibers in which a dehalogenation treatment step and a reduction treatment step are simultaneously performed in the same bath, In addition, the present invention relates to a method for reducing oxidized cellulose fibers in which a dehalogenation treatment step and a reduction treatment step are simultaneously performed in the same bath on the oxidized cellulose fibers.
  • cotton apparel products such as underwear (cellulose fiber products) have been required to have high moisture absorption and moisture release properties.
  • Examples of a method for obtaining a cotton apparel product (cellulose fiber product) having such a high hygroscopic property and moisture releasing property include a method of hydrophilizing cellulose fiber as a raw material.
  • Various methods for hydrophilizing cellulose fibers are known. A typical example is a method of oxidizing a hydroxyl group of cellulose to a carboxyl group.
  • a reaction solution containing an N-oxyl compound such as 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and a halogen-based oxidizing agent is used.
  • TEMPO 2,2,6,6-tetramethylpiperidine-N-oxyl
  • a halogen-based oxidizing agent is used.
  • a method of performing an oxidation treatment for oxidizing raw material cellulose fibers is known. Further, a dehalogenation treatment for removing halogen remaining in the oxidized cellulose is performed, and a reduction treatment for reducing a ketone group present at the 2-position and / or 3-position of the glucose unit, which is produced by producing the oxidized cellulose fiber, is also performed.
  • the method of performing is known (for example, patent document 1).
  • the dehalogenation treatment step and the reduction treatment step were performed separately in separate baths.
  • the dehalogenating agent used in the dehalogenation treatment process uses an oxidizing agent such as hydrogen peroxide, and if the dehalogenation treatment and the reduction treatment are carried out simultaneously, the reducing agent used in the reduction treatment step is used. It was thought that the oxidation-reduction reaction occurred and neither the dehalogenation treatment nor the reduction treatment of the oxidized cellulose fiber was sufficiently performed.
  • the present invention is capable of sufficiently removing halogen remaining in oxidized cellulose by simultaneously performing dehalogenation treatment and reduction treatment in the same bath, and producing oxidized cellulose fibers. It was found that the ketone group existing at the 2-position and / or 3-position of the glucose unit produced by the above can be sufficiently reduced.
  • the present invention can suppress a decrease in the degree of polymerization of the oxidized cellulose fiber in oxidized cellulose obtained by oxidizing the carbon at the 6-position of the glucose unit in the raw cellulose fiber to a carboxyl group, and whiteness. It aims at providing the manufacturing method of the hydrophilic cellulose fiber which does not fall.
  • the inventors of the present invention have made extensive studies to solve the above-mentioned problems.
  • the dehalogenation treatment step and the reduction treatment step which have been conventionally performed separately in separate baths, are simultaneously performed to polymerize oxidized cellulose fibers. It has been found that hydrophilic cellulose fibers can be obtained in which the decrease in the degree of whiteness can be suppressed and the degree of whiteness does not decrease.
  • the present invention has been completed based on such findings.
  • a dehalogenating agent, a reducing agent, and oxidized cellulose fiber are mixed to perform a dehalogenation treatment to remove halogen remaining in the oxidized cellulose fiber, and at the second position and / or 3 of the glucose unit of the oxidized cellulose fiber.
  • Item 2 The hydrophilicity according to Item 1, wherein the step (A) is a step of performing a dehalogenation treatment by adding an oxidized cellulose fiber in a reaction solution containing a dehalogenating agent and a reducing agent, and performing a reduction treatment.
  • a method for producing a modified cellulose fiber is a step of performing a dehalogenation treatment by adding an oxidized cellulose fiber in a reaction solution containing a dehalogenating agent and a reducing agent, and performing a reduction treatment.
  • Item 3. The hydrophilized cellulose according to Item 1 or 2, wherein the dehalogenating agent is at least one selected from the group consisting of hydrogen peroxide, ozone, sodium peroxide, sodium perboride, sodium percarbonate, and peracetic acid. A method for producing fibers.
  • the reducing agent is at least one selected from the group consisting of thiourea, hydrosulfite, sodium hydrogen sulfite, sodium borohydride, sodium cyanoborohydride, lithium borohydride, acidic sodium sulfite, and thiourea dioxide.
  • Item 4. The method for producing a hydrophilic cellulose fiber according to any one of Items 1 to 3.
  • Item 5 The method for producing a hydrophilic cellulose fiber according to any one of Items 2 to 4, wherein the pH of the reaction solution in the step (A) is 7 to 12.
  • Item 6. The method for producing hydrophilic cellulose fibers according to any one of Items 2 to 5, wherein the temperature of the reaction solution in the step (A) is 10 to 90 ° C.
  • Item 7 Oxidized cellulose (1) The hydrophilicity according to any one of Items 1 to 6, obtained by a first oxidation treatment step of oxidizing cellulose fibers in a reaction solution containing an N-oxyl compound and an oxidizing agent of the N-oxyl compound. A method for producing cellulose fibers.
  • Item 8 The method for producing a hydrophilic cellulose fiber according to Item 7, wherein the oxidizing agent is hypohalous acid, halogenated isocyanuric acid or a salt thereof.
  • Item 9 Oxidized cellulose (2) Aldehyde groups present in the oxidized cellulose fiber obtained in the step (1) by oxidizing the oxidized cellulose fiber obtained in the step (1) in a second reaction solution containing an oxidizing agent.
  • Item 9 The method for producing a hydrophilic cellulose fiber according to Item 7 or 8 obtained by the second oxidation treatment step for oxidizing the oxidant.
  • Item 10 The method for producing a hydrophilic cellulose fiber according to any one of Items 7 to 9, further comprising a cocatalyst in the first reaction solution in the step (1).
  • Item 11 The method for producing a hydrophilic cellulose fiber according to Item 9 or 10, wherein the oxidizing agent in the step (2) is a halogen acid oxidizing agent.
  • a dehalogenating agent, a reducing agent, and oxidized cellulose fiber are mixed to perform a halogen removal treatment to remove the halogen remaining in the oxidized cellulose fiber, and at the 2nd and / or 3rd position of the glucose unit of the oxidized cellulose fiber.
  • the method for producing a hydrophilic cellulose fiber of the present invention it is possible to suppress a decrease in the degree of polymerization of the oxidized cellulose fiber in the oxidized cellulose obtained by oxidizing the 6-position carbon of the glucose unit in the raw cellulose fiber to a carboxyl group. It is possible to obtain a hydrophilic cellulose fiber that can be reduced and does not have a reduced whiteness.
  • the raw material cellulose fiber used in the method for producing a hydrophilic cellulose fiber of the present invention may be a natural cellulose fiber such as a plant, animal or bacteria-producing gel, or a regenerated cellulose fiber.
  • natural cellulose fibers such as cotton, hemp, pulp, and bacterial cellulose
  • regenerated cellulose fibers such as rayon and cupra can be used.
  • the form of the raw material cellulose fiber is not limited to a fabric such as a woven or knitted fabric or a non-woven fabric, but may be a filamentous material such as a filament, a staple, or a string.
  • the structural structure of the fiber may be a blended fiber, a blended fiber, a blended fabric, a woven fabric, or a knitted fabric.
  • the raw material cellulose fiber is preferably washed and scoured in advance from the viewpoint that the cellulose fiber can be sufficiently made hydrophilic in the subsequent steps and the bleaching effect can be sufficiently exhibited.
  • “scouring” refers to a process of removing impurities contained in natural fibers, oil added at the spinning and knitting stage, machine oil adhering to the work process, iron rust, and the like.
  • the oxidation obtained by performing the first oxidation treatment in the step (1) and the second oxidation treatment in the step (2) are preferred.
  • step (1) and step (2) will be described.
  • Step (1) is a step of oxidizing cellulose fibers in a first reaction solution containing an N-oxyl compound and an oxidizing agent.
  • the N-oxyl compound contained in the first reaction solution is used as a catalyst when oxidizing the cellulose fibers.
  • Specific examples of the N-oxyl compound include those represented by the general formula (I):
  • R 1 to R 4 are the same or different and each represents an alkyl group having about 1 to 4 carbon atoms
  • R 5 and R 6 are the same or different and each represents a hydrogen atom; an acetylamino group; Carboxyl group; phosphonooxy group; amino group; 2-halogenated acetylamino group substituted by halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom); hydroxy group; alkoxy having about 1 to 4 carbon atoms
  • An adamantane group, and R 5 and R 6 may be bonded to each other by an oxygen atom to form an oxo group
  • R 7 and R 8 are the same or different and each represents a hydrogen atom or an alkyl group having about 1 to 4 carbon atoms.) Etc.
  • N-oxyl compounds include 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), TEMPO derivatives having various functional groups at the 4-position carbon of TEMPO, 2-azaadamantane- N-oxyl and the like can be mentioned.
  • TEMPO 2,2,6,6-tetramethylpiperidine-N-oxyl
  • 2-azaadamantane- N-oxyl and the like can be mentioned.
  • TEMPO derivative examples include 4-acetamido TEMPO, 4-carboxy TEMPO, 4-phosphonooxy TEMPO, 4-amino-TEMPO, 4- (2-bromoacetamido) -TEMPO, 4-hydroxy TEMPO, 4-oxy TEMPO, 4-methoxy TEMPO, etc. are mentioned.
  • TEMPO 4-methoxy TEMPO
  • 4-acetamido TEMPO are preferable in that the reaction rate for oxidizing the carbon at the 6-position of the glucose unit of the cellulose fiber is high.
  • the catalyst content of the N-oxyl compound is sufficient, and specifically, it is preferably about 0.01 to 3 g / L in the reaction solution. Further, the content of the N-oxyl compound is more preferably about 0.1 to 2 g / L because it does not greatly affect the degree of hydrophilic treatment and the quality of the obtained cellulose fiber.
  • the content ratio of the N-oxyl compound in the reaction solution is preferably about 0.03 to 9.0% owf, more preferably about 0.75 to 6.0% owf.
  • the unit “% owf” represents the weight relative to 1 g of fiber.
  • hypohalous acid halogenated isocyanuric acid or a salt thereof is preferable.
  • halogen in the hypohalous acid examples include chlorine, bromine, and iodine, and specific examples include hypochlorous acid, hypobromous acid, and hypoiodous acid.
  • the metal salt forming the hypohalite examples include alkali metal salts such as lithium, potassium and sodium; alkaline earth metal salts such as calcium, magnesium and strontium. Moreover, the salt of ammonium and hypohalous acid is also mentioned.
  • hypochlorous acid lithium hypochlorite, potassium hypochlorite, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, strontium hypochlorite, etc.
  • examples thereof include ammonium hypochlorite and the like.
  • hypobromite and hypoiodite corresponding to these can also be used.
  • a preferable oxidant in the first oxidation step is an alkali metal hypohalite, and a more preferable oxidant is an alkali metal hypochlorite (such as sodium hypochlorite). is there.
  • A represents a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; an alkali metal or an alkaline earth metal, and X represents the same or different, each representing a fluorine atom.
  • Halogen atoms such as chlorine atom, bromine atom and iodine atom.
  • the halogenated isocyanuric acid represented by the formula (1) or a salt thereof is used.
  • Examples of the alkali metal that forms the halogenated isocyanurate include lithium, potassium, and sodium, and examples of the alkaline earth metal that forms the halogenated isocyanurate include calcium, magnesium, and strontium. Moreover, the salt of ammonium and halogenated isocyanuric acid is also mentioned.
  • halogenated isocyanuric acid examples include dichloroisocyanuric acid and trichloroisocyanuric acid.
  • halogenated isocyanurate examples include sodium dichloroisocyanurate. Of these, sodium dichloroisocyanurate and sodium dichloroisocyanurate dihydrate are preferred because of their high solubility in water and excellent bleaching and bactericidal effects in water.
  • the content of the oxidizing agent in the reaction solution is preferably about 0.03 to 10 g / L, more preferably about 1.0 to 5.0 g / L.
  • the content of the oxidizing agent is preferably about 0.1 to 30% owf, and more preferably about 3.0 to 15% owf.
  • an N-oxyl compound and a promoter may be used as a catalyst component.
  • the cocatalyst include a salt of halogen and alkali metal (alkali metal salt), a salt of halogen and alkaline earth metal (alkaline earth metal salt), ammonium salt, sulfate and the like.
  • the halogen for forming the alkali metal salt, alkaline earth metal salt, or ammonium salt include chlorine, bromine, and iodine.
  • Examples of the alkali metal that forms the alkali metal salt include lithium, potassium, and sodium.
  • the alkaline earth metal forming the alkaline earth metal salt include calcium, magnesium, strontium and the like.
  • ammonium salts include ammonium bromide, ammonium iodide, and ammonium chloride.
  • sulfates include sulfates such as sodium sulfate (sodium salt), sodium hydrogen sulfate, and alum. These promoters can be used alone or in combination of two or more. These cocatalysts may form hydrates.
  • the pH of the first reaction solution in the first oxidation treatment of step (1) is maintained at about 4 to 12, which is a pH suitable for the oxidized N-oxyl compound to act on cellulose fibers. It is preferable to maintain the pH at about 8-11.
  • the pH of the first reaction solution may be a basic substance (ammonia, potassium hydroxide, sodium hydroxide, etc.) or an acidic substance (acetic acid, oxalic acid, succinic acid, glycolic acid, malic acid, citric acid, benzoic acid, etc.) It can be adjusted by appropriately adding an acid or an inorganic acid such as nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid).
  • an acid or an inorganic acid such as nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid.
  • a penetrant may be further added to the first reaction solution used in the first oxidation treatment in the step (1).
  • penetrant known ones used for cellulose fibers can be applied. Specifically, anionic surfactants (carboxylates, sulfate esters, sulfonates, phosphate ester salts, etc.) Nonionic surfactants (polyethylene glycol type, other alcohol type, etc.) can be mentioned, and for example, Sintole (trade name: manufactured by Takamatsu Yushi Co., Ltd.) and the like can be used.
  • the drug By adding a penetrant to the first reaction solution, the drug can penetrate into the inside of the cellulose fiber, and more carboxyl groups (aldehyde groups) can be introduced to the surface of the cellulose fiber. Thereby, the hydrophilicity (hygroscopicity) of a cellulose fiber can be improved more.
  • the procedure for oxidizing the cellulose fibers is not particularly limited, but first, an N-oxyl compound and a promoter are added to the reaction solvent, and the cellulose fibers are further immersed, and then an oxidizing agent is added. It is preferable to add.
  • an N-oxyl compound and a promoter are added to the reaction solvent, and the cellulose fibers are further immersed, and then an oxidizing agent is added. It is preferable to add.
  • the N-oxyl compound and the co-catalyst permeate the cellulose fiber, so that the effect of hydrophilic treatment can be obtained without processing unevenness.
  • the bath ratio of the first reaction solution and the cellulose fiber used in the first oxidation treatment is preferably about 10 to 100 g, more preferably about 15 to 30 g, with respect to 1 g of cellulose fiber. It is more preferable.
  • the first reaction solution By setting the first reaction solution to about 15 g or more with respect to 1 g of cellulose fibers, an effect that the contact efficiency between the cellulose fibers and the reaction solution is improved can be obtained.
  • maintained by setting a 1st reaction solution to about 30 g or less with respect to 1 g of cellulose fibers is acquired.
  • the temperature of the first oxidation treatment in the step (1) is preferably about 0 ° C. or higher from the viewpoint that COOH groups can be sufficiently introduced, oxidant evaporation can be prevented, and effective chlorine can be retained. The above is more preferable. Further, the temperature of the first oxidation treatment in the step (1) is preferably about 50 ° C. or less, more preferably about 30 ° C. or less, from the viewpoint of not decreasing the degree of polymerization of cellulose and inhibiting embrittlement of cellulose fibers. preferable.
  • the time of the first oxidation treatment in the step (1) is preferably about 1 minute or more from the viewpoint that a COOH group can be sufficiently introduced and a time for starting a reaction cycle is required. More than about is more preferable. Further, the time of the first oxidation treatment in the step (1) is preferably about 30 minutes or less, more preferably about 15 minutes or less from the viewpoint of the degree of polymerization of cellulose not decreasing and the suppression of embrittlement of cellulose fibers. preferable.
  • an unreacted oxidant (subhalogenic acid or a salt thereof, halogenated siasocyanuric acid or a salt thereof, or a subhalogenic acid or a salt thereof decomposed from a halogenated siasocyanuric acid or a salt thereof, etc., as necessary It is preferable to carry out a treatment for removing), and then repeat washing with water.
  • Step (2) (second oxidation treatment)
  • the oxidized cellulose fiber obtained in the step (1) is oxidized in the second reaction solution containing an oxidizing agent, so that the oxidized cellulose fiber obtained in the step (1) is oxidized. It is a step of oxidizing existing aldehyde groups.
  • the primary hydroxyl group of the glucose unit located on the microfibril surface of the cellulose fiber is selectively oxidized to a carboxyl group, but some aldehyde groups are formed in addition to the carboxyl group.
  • the Formation of this aldehyde group causes a beta elimination reaction or coloring during heating, leading to a decrease in strength due to the low molecular weight of the cellulose fiber.
  • the aldehyde group generated by the first oxidation treatment in the step (1) is oxidized to a carboxyl group to obtain an oxidized cellulose fiber containing no aldehyde group.
  • the raw material used in the second oxidation treatment in step (2) is oxidized cellulose fiber obtained by the first oxidation step.
  • the oxidizing agent used in the second oxidation treatment in step (2) is an oxidizing agent that can oxidize aldehyde groups and convert them into carboxyl groups. Specifically, halous acid or a salt thereof (chlorous acid or a salt thereof, bromous acid or a salt thereof, iodic acid or a salt thereof), a peracid (hydrogen peroxide, peracetic acid, persulfuric acid, perbenzoic acid) Acid, etc.). These oxidizing agents can be used alone or in combination of two or more. Further, it may be used in combination with an oxidase such as laccase.
  • the content of the oxidizing agent can be appropriately set, but is preferably in the range of 0.01 to 50 mmol / g with respect to the cellulose fiber.
  • Examples of the halogen in the halite include chlorine, bromine and iodine.
  • Examples of the salt for forming the halite include alkali metal salts such as lithium, potassium and sodium; alkalis such as calcium, magnesium and strontium. Earth metal salt; ammonium salt and the like. More specific examples of the halite include lithium chlorite, potassium chlorite, sodium chlorite, calcium chlorite, magnesium chlorite, strontium chlorite, etc. An example is ammonium chlorate. In addition, bromite and iodate corresponding to these can also be used.
  • an alkali metal halite is used, and an alkali metal chlorite is more preferably used.
  • the content of the oxidizing agent in the reaction solution is preferably about 1 to 90 g / L, and more preferably about 2 to 20 g / L.
  • the content ratio of the oxidizing agent is set to about 2 g / L or more, an effect of bleaching cellulose fibers can be obtained in addition to the aldehyde group oxidizing effect.
  • the effect which suppresses the embrittlement of the cellulose fiber by chlorine of an oxidizing agent is acquired by setting the content rate of an oxidizing agent to about 20 g / L or less.
  • the content of the oxidizing agent is preferably about 2 to 180% owf, more preferably about 4 to 40% owf.
  • the pH of the reaction solution is preferably maintained in a neutral to acidic range.
  • a more specific pH is preferably in the range of 3-7.
  • a buffer solution it is also preferable to further add a buffer solution to the second reaction solution.
  • a buffer solution various buffer solutions such as a phosphate buffer solution, an acetate buffer solution, a citrate buffer solution, a borate buffer solution, a tartaric acid buffer solution, and a Tris buffer solution can be used.
  • the buffer solution By using the buffer solution, it is possible to suppress a change in pH in the reaction solution, and it is not necessary to continuously add acid or alkali to maintain the pH.
  • the bath ratio of the second reaction solution and cellulose fibers used in the second oxidation treatment is preferably about 5 to 100 g of the second reaction solution with respect to 1 g of cellulose fibers, and about 10 to 30 g. It is more preferable.
  • the second reaction solution By setting the second reaction solution to about 5 g or more with respect to 1 g of the cellulose fiber, an effect that the contact efficiency between the cellulose fiber and the reaction solution is improved can be obtained.
  • maintained by setting a 2nd reaction solution to about 100 g or less with respect to 1 g of cellulose fibers is acquired.
  • a chelating agent, a surfactant, a penetrating agent, and the like may be added as appropriate in order to improve the effect of inhibiting embrittlement of cellulose fibers by metals.
  • the temperature of the second oxidation treatment in the step (2) is preferably about 60 ° C. or higher from the viewpoint of sufficiently oxidizing the aldehyde group to a COOH acid group and exhibiting the bleaching effect of the cellulose fiber, and about 70 ° C. The above is more preferable. Further, the temperature of the second oxidation treatment in the step (2) is preferably about 98 ° C. or less from the viewpoint that the degree of polymerization of cellulose does not decrease, the suppression of embrittlement of cellulose fibers by chlorine as an oxidizing agent, and the like. It is more preferable that the temperature is about 0 ° C. or less.
  • the time of the second oxidation treatment in the step (2) is preferably about 30 minutes or more from the viewpoint that the aldehyde group can be sufficiently oxidized to the COOH acid group and the bleaching effect of the cellulose fiber can be exhibited, and about 50 minutes. The above is more preferable. Further, the time of the second oxidation treatment in the step (2) is preferably about 120 minutes or less from the viewpoint that the degree of polymerization of cellulose does not decrease, the suppression of embrittlement of cellulose fibers by chlorine as an oxidizing agent, and the like. More preferably, it is less than about minutes.
  • the reaction vessel can be hermetically sealed, so that a pressure device for pressurizing the inside of the reaction vessel may be provided for the oxidation treatment.
  • step (2) After completion of the oxidation treatment in step (2), it is preferable to stop the oxidation reaction as necessary and repeat washing with water.
  • Step (A) is a step of simultaneously performing dehalogenation treatment and reduction treatment on the oxidized cellulose fiber.
  • Halogen may remain in the oxidized cellulose fiber due to the halogen-based oxidizing agent used when the raw material cellulose fiber is oxidized to obtain the oxidized cellulose fiber.
  • the dehalogenation process is a process of removing the halogen remaining in such oxidized cellulose fiber.
  • a carboxyl group can be introduced into the surface of the cellulose fiber, but the oxidation treatment may further cause yellowing (decrease in whiteness). This is considered to be because not only the carboxylation of carbon at the 6th position of the cellulose fiber but also the carbon at the 2nd or 3rd position is partially oxidized to produce a ketone. Therefore, by performing a reduction treatment with a reducing agent, it is possible to reduce the produced ketone and suppress yellowing (decrease in whiteness) of the hydrophilic cellulose fiber.
  • a dehalogenating agent, a reducing agent, and oxidized cellulose fibers are mixed, and a dehalogenation treatment is performed to remove halogen remaining in the oxidized cellulose fibers. And / or a reduction process for reducing a ketone group present at the 3-position.
  • dehalogenating agent examples include hydrogen peroxide, ozone, sodium peroxide, sodium perboride, sodium percarbonate, peracetic acid, dehalogenase, calcium sulfite, ascorbic acid and the like.
  • Hydrogen peroxide and ozone are used as a hydrogen peroxide solution and an ozone solution, respectively.
  • the concentration of the dehalogenating agent in the reaction solution used in step (A) depends on the type of dehalogenating agent, but is preferably about 0.1 to 100 g / L in the reaction solution, for example, 0.67 to About 10 g / L is more preferable.
  • the content ratio of the dehalogenating agent is preferably about 1 to 300% owf, more preferably about 2 to 30% owf.
  • Examples of the reducing agent include those that can reduce partially generated ketone groups to alcohols, and those that do not reduce the generated carboxyl groups.
  • Specific examples include thiourea, hydrosulfite, and bisulfite.
  • Examples thereof include sodium, sodium borohydride, sodium cyanoborohydride, lithium borohydride, acidic sodium sulfite (sodium bisulfite), and thiourea dioxide.
  • sodium borohydride and sodium hydrogen sulfite are preferable from the viewpoint of excellent initial whiteness and whiteness reduction suppression.
  • the concentration of the reducing agent contained in the reaction solution is preferably about 0.02 to 4 g / L, and more preferably about 0.2 to 2 g / L. By setting the concentration within the above range, an effect of suppressing fabric embrittlement due to an excessive reducing agent can be obtained.
  • the content of the reducing agent is preferably about 0.06 to 12% owf, more preferably about 0.6 to 6.0% owf.
  • the pH of the reaction solution used in the step (A) is preferably about 7 or more, preferably about 7.5 or more from the viewpoint that the oxidizing agent remaining in the oxidized cellulose fiber can be neutralized and good in reducing agent activity maintenance. Is more preferable, and about 8 or more is more preferable. Further, the pH of the reaction solution when performing the reduction treatment with the reducing agent is preferably about 12 or less, more preferably about 11 or less, more preferably about 10 or less from the viewpoint that the embrittlement due to the alkaline side can be suppressed. Is more preferable.
  • the pH of the reaction solution can be adjusted by appropriately adding aqueous ammonia, hydrochloric acid, soda ash, NaOH, KOH and the like.
  • the reaction solution with respect to 1 g of the cellulose fiber is preferably about 5 to 100 g, and more preferably about 5 to 50 g.
  • the reaction solution By setting the reaction solution to about 5 g or more with respect to 1 g of cellulose fiber, the liquid contact of the reaction solution with respect to the cellulose fiber is improved, and the effect of neutralizing the oxidizing agent remaining in the cellulose fiber is obtained.
  • the reaction solution By setting the reaction solution to about 100 g or less with respect to 1 g, an effect of maintaining the stirring efficiency of the cellulose fiber and the reaction solution can be obtained.
  • the treatment temperature in the step (A) is preferably about 10 ° C. or more, more preferably about 20 ° C. or more from the viewpoint that the effect of dechlorination can be exhibited and the reduction reaction can proceed favorably.
  • a processing temperature in a process (A) about 90 degrees C or less is preferable and about 80 degrees C or less is more preferable from a viewpoint that degradation of the cellulose fiber by alkalinity is suppressed.
  • the treatment time for step (A) is preferably about 5 minutes or more, more preferably about 10 minutes or more. Further, the treatment time of the step (A) is preferably about 60 minutes or less, more preferably about 40 minutes or less from the viewpoint of fabric embrittlement and curing when exposed to alkaline conditions for a long time.
  • the hydrophilic cellulose fiber (oxidized cellulose fiber) obtained by the hydrophilic treatment method of the present invention described above is one in which at least a part of hydroxyl groups located on the microfibril surface of cellulose are oxidized only by carboxyl groups. It is. Or it can specify as a cellulose fiber whose content of an aldehyde group is less than 0.05 mmol / g.
  • the above hydrophilic cellulose fiber has no or no 6-position carbon aldehyde group on the surface of cellulose microfibrils.
  • the case where it can be regarded that there is no aldehyde group corresponds to the content of the aldehyde group being less than 0.05 mmol / g.
  • the amount of the aldehyde group is more preferably 0.01 mmol / g or less, and still more preferably 0.001 mmol / g or less.
  • the amount of aldehyde group can be measured, for example, by the following procedure.
  • a hydrophilic cellulose fiber sample precisely weighed in dry weight is put in water, and the pH is adjusted to about 2.5 with a 0.1 M aqueous hydrochloric acid solution. Measure the degree. The measurement is continued until the pH is 11. Then, the amount of functional group is determined from the amount of sodium hydroxide (sodium hydroxide solution amount) (V) consumed in the weak acid neutralization stage where the change in electrical conductivity is gradual, using the following equation. This amount of functional groups is the amount of carboxyl groups.
  • Functional group amount (mmol / g) V (ml) ⁇ 0.05 / mass of cellulose (g)
  • a sample of hydrophilic cellulose fiber used for measurement of the amount of carboxyl groups was further oxidized at room temperature for 48 hours in a 2% aqueous sodium chlorite solution adjusted to pH 4 to 5 with acetic acid. Measure. An amount obtained by subtracting the amount of the carboxyl group from the measured amount of the functional group is the amount of the aldehyde group.
  • the present invention mixes a dehalogenating agent, a reducing agent, and oxidized cellulose fiber, performs a dehalogenation treatment to remove halogen remaining in the oxidized cellulose fiber,
  • the present invention also relates to a method for reducing oxidized cellulose fiber that reduces a ketone group present at the 3-position.
  • the primary hydroxyl group of the glucose unit obtained by the first oxidation treatment in the step (1) and the second oxidation treatment in the step (2) is selectively converted into a carboxyl group.
  • the cellulose fiber is made of ozone, sodium hypochlorite, calcium hypochlorite, sodium chlorite.
  • the dehalogenation treatment and the method for reducing the ketone group present at the 2-position and / or 3-position of the glucose unit of the oxidized cellulose fiber are carried out by the same methods as the dehalogenation treatment and the reduction treatment in the step (A). Can do.
  • the hydrophilic cellulose fiber obtained by the method for producing hydrophilic cellulose fiber of the present invention does not substantially contain a carbon in which the 6-position is an aldehyde group, the colored component derived from the aldehyde group even when subjected to heat treatment Is hard to generate. Therefore, the hydrophilic cellulose fiber obtained by the above production method is a material suitable for use in clothing such as underwear that requires high whiteness. In addition, since quality does not deteriorate due to heat, it is a material that is easy to handle without any restrictions in processing.
  • the hydrophilic cellulose fiber obtained by the above-described production method is less likely to cause breakage of cellulose microfibrils by aldehyde groups in the production process, and therefore has improved hygroscopicity without substantially impairing the strength of the raw material cellulose fiber. It has become.
  • the hydrophilic cellulose fiber in which the primary hydroxyl group of cellulose microfibril is oxidized to a carboxyl group can obtain a high heat dissipation effect and heat generation effect due to its high hygroscopicity, and is suitably used for various fiber products. be able to.
  • textile products examples include clothing supplies, miscellaneous goods, interior goods, bedding goods, and industrial materials.
  • the above clothing items include outing clothing, sportswear, homewear, relax wear, pajamas, sleepwear, underwear, office wear, work clothes, food lab coats, nursing lab coats, patient garments, nursing garments, student garments, kitchen garments, etc.
  • Examples of the underwear include shirts, briefs, shorts, girdle, pantyhose, tights, socks, leggings, belly rolls, steteco, patches, petticoats, and the like.
  • miscellaneous goods include apron, towel, gloves, muffler, hat, shoes, sandals, bag, umbrella and the like.
  • bedding products include futon side, futon stuffed blanket, blanket side, pillow filling, sheets, waterproof sheets, duvet cover, pillow covers and the like.
  • the above-mentioned industrial materials include filters.
  • step (1) With the reaction solution and reaction conditions shown in Table 1, the dough (cellulose fiber) was treated with 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and sodium hypochlorite (NaClO) in the following procedure. A first oxidation treatment was performed. As the fabric, 100% cotton knitted fabric (40th milling fabric) was used.
  • TEMPO 2,2,6,6-tetramethylpiperidine-N-oxyl
  • NaClO sodium hypochlorite
  • TEMPO shown in Table 1 and sodium bromide (NaBr) were dissolved in water, and the dough was sufficiently immersed in the obtained solution.
  • NaClO was further added while adjusting the pH as shown in Table 1, and the first oxidation treatment was performed under the conditions shown in Table 1.
  • NaClO uses a 5 wt% aqueous solution, and the blending amounts and blending ratios in Table 1 indicate the blending amounts and blending ratios of the 5 wt% NaClO aqueous solution.
  • step (2) The first oxidation treatment in the step (1) and each sample fabric washed with water were further subjected to a second oxidation treatment with sodium chlorite (NaClO 2 ) under the reaction solutions and reaction conditions shown in Table 2.
  • NaClO 2 sodium chlorite
  • CG1000 in Table 2 is a chelating agent Neocrystal (manufactured by Nikka Chemical Co., Ltd.) for bleaching chlorine
  • NaClO 2 uses a 25% by weight aqueous solution.
  • the compounding quantity and compounding ratio of a 25 wt% aqueous solution of NaClO 2 are shown.
  • each sample was taken out, washed with hot water at 60 ° C., and further washed with water.
  • Process (A) A reaction solution containing hydrogen peroxide (H 2 O 2 ) and sodium borohydride (NaBH 4 ) shown in Tables 3 and 6 was prepared, and the reaction solution was subjected to the second oxidation treatment, hot water washing, and The sample fabrics that had been washed with water were placed, and under the reaction conditions shown in Tables 3 and 6, dechlorination treatment with H 2 O 2 and reduction treatment with NaBH 4 were simultaneously performed.
  • H 2 O 2 hydrogen peroxide
  • NaBH 4 sodium borohydride
  • PLC7000 in Table 3 is a polycarboxylic acid chelating agent neolate (manufactured by Nikka Chemical Co., Ltd.), H 2 O 2 uses a 35 wt% aqueous solution, and the blending amount and blending ratio in Table 3 are shows the amount and proportion of 35 wt% aqueous solution of H 2 O 2.
  • each sample was taken out, washed with 60 ° C. water, and further washed with water.
  • step (A) Each sample material after the dechlorination and reduction treatment (step (A)) was neutralized with 1.0 mol / L hydrochloric acid so that the pH was 4.
  • Table 6 shows the amount of carboxyl groups (the amount of COOH groups), the degree of polymerization, and the degree of polymerization for each sample dough (Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-4) manufactured by the above manufacturing process. And a decrease in whiteness.
  • the amount of carboxyl groups was measured by conductometric titration, and the degree of polymerization was measured by the following method.
  • the fibers collected from each of the sample fabrics were reduced with sodium borohydride in advance to reduce residual aldehyde groups to alcohol, and this was dissolved in a 0.5 M copper ethylenediamine solution, and the degree of polymerization was determined by a viscosity method. .
  • the copper ethylenediamine solution is alkaline, and if aldehyde groups remain in the oxidized cellulose, a beta elimination reaction may occur in the dissolution process and the molecular weight may decrease.
  • the aldehyde group was converted to an alcoholic hydroxyl group.
  • the formula for determining the degree of polymerization of cellulose from the viscosity of cellulose dissolved in 0.5 M copper ethylenediamine solution is “Isogai, A., Mutoh, N., Onabe, F., Usuda, M.,“ Viscosity measurements. of cellulose / SO 2 -amine-dimethylsulfoxide solution ”, Sen'i Gakkaishi, 45, 299-306 (1989).”
  • the whiteness is calculated as L * -3b * from the CIELAB color system (measured by Macbeth WHITE-EYE3000 micro area manufactured by Kollmorgen Instruments Corporation), and the difference between the whiteness of each sample before and after drying was measured as the degree of whiteness reduction.
  • the whiteness after absolutely dry is the whiteness after the absolute dry weight is measured based on “JIS L-0105 4.3”.
  • the “post-bleached cotton cloth” shown in Table 6 is a cotton cloth obtained by scouring a 40th milling dough, bleaching it with NaClO 2 treatment and H 2 O 2 treatment, dehydrating and drying.
  • Table 6 shows the treatment temperature in the dechlorination and reduction treatment (step (A)), the concentration of NaBH 4 , and the evaluation results of the obtained sample dough.
  • Comparative Example 1-2 in which the dechlorination treatment with H 2 O 2 and the reduction treatment with NaBH 4 were performed in a separate bath at 50 ° C., the same results as in Comparative Example 1-1 were obtained.
  • Comparative Example 1-3 in which the reduction treatment with NaBH 4 was not performed and only the dechlorination treatment with H 2 O 2 was performed, a large decrease in whiteness occurred, and conversely, the dechlorination treatment with H 2 O 2 was not performed. It can be seen that also in Comparative Example 1-4 in which the reduction treatment with NaBH 4 was performed at 25 ° C., the degree of polymerization and the degree of whiteness were reduced as compared with Examples 1-1 to 1-3. .
  • Example 2 In the first oxidation treatment, which is the step (1), except that the first oxidation treatment with TEMPO of the dough (cellulose fiber) and sodium dichloroisocyanurate (SDIC) was performed with the reaction solution and reaction conditions shown in Table 7 Produced a hydrophilic cellulose fiber in the same manner as in Example 1.
  • Example 2 using SDIC as the oxidizing agent in the first oxidation treatment, similarly to Example 1, dechlorination treatment with H 2 O 2 and reduction treatment with NaBH 4 were simultaneously performed in the same bath. When it does, it turns out that the fall of the polymerization degree and whiteness of an oxidized cellulose fiber can be suppressed, without reducing the amount of COOH groups.

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Abstract

La présente invention concerne un procédé de production d'une fibre cellulosique hydrophilisée capable de supprimer la diminution du degré de polymérisation d'une fibre cellulosique oxydée, ladite cellulose oxydée étant obtenue par oxydation du carbone dans la position 6 d'une unité de glucose d'une fibre cellulosique de matériau de départ dans un groupe carboxyle, et ne diminuant pas le degré de blancheur. Le procédé de production d'une fibre cellulosique hydrophilisée comprend (A) une étape au cours de laquelle un traitement de déshalogénisation est effectué par mélange d'un agent de déshalogénisation, d'un réducteur et d'une fibre cellulosique oxydée de manière à éliminer un halogène restant dans la fibre cellulosique oxydée. Un traitement de réduction destiné à réduire un groupe cétone présent dans la position 2 et/ou la position 3 d'une unité de glucose de la fibre cellulosique oxydée est également réalisé.
PCT/JP2012/050992 2011-01-26 2012-01-18 Procédé de production d'une fibre cellulosique hydrophilisée et procédé de réduction d'une fibre cellulosique oxydée WO2012102153A1 (fr)

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EP12739540.8A EP2669425A1 (fr) 2011-01-26 2012-01-18 Procédé de production d'une fibre cellulosique hydrophilisée et procédé de réduction d'une fibre cellulosique oxydée
CN201280005803.5A CN103328715B (zh) 2011-01-26 2012-01-18 生产亲水化纤维素纤维的方法以及将氧化纤维素纤维还原的方法
JP2012554743A JP5774031B2 (ja) 2011-01-26 2012-01-18 親水性化セルロース繊維の製造方法、及び酸化セルロース繊維の還元方法
US13/993,448 US9296829B2 (en) 2011-01-26 2012-01-18 Method for producing hydrophilized cellulose fiber, and method for reducing oxidized cellulose fiber
KR1020137022050A KR20140003559A (ko) 2011-01-26 2012-01-18 친수성화 셀룰로오스 섬유의 제조 방법 및 산화 셀룰로오스 섬유의 환원 방법

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CN103275230A (zh) * 2013-05-15 2013-09-04 威高集团有限公司 一种改善氧化再生纤维素羧酸钠止血材料的贮存稳定性的方法
JPWO2016186055A1 (ja) * 2015-05-15 2018-03-08 日本製紙株式会社 アニオン変性セルロースナノファイバー分散液および組成物

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US20160010279A1 (en) 2013-12-06 2016-01-14 University Of Maryland At College Park Scalable, highly transparent paper with microsized fiber
DE102014207673A1 (de) * 2014-04-24 2015-10-29 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel mit elektrochemisch aktivierbarer anionischer Mediatorverbindung
CN104017090B (zh) * 2014-05-05 2016-06-22 华南理工大学 一种采用过氧化氢制备羧基纤维素的方法
FI20146116A (fi) * 2014-12-18 2016-06-19 Upm Kymmene Corp Menetelmä ja laitteisto selluloosan katalyyttisen hapetuksen säätämiseksi
WO2017075417A1 (fr) 2015-10-28 2017-05-04 Innotech Materials, Llc Préparation de cellulose modifiée et ses dérivés
WO2017214477A1 (fr) * 2016-06-09 2017-12-14 Board Of Regents, The University Of Texas System Recyclage du coton
WO2020059525A1 (fr) * 2018-09-21 2020-03-26 東洋製罐グループホールディングス株式会社 Nanocellulose et procédé pour la production de celle-ci
CN111333690B (zh) * 2018-12-18 2021-10-08 奥锐特药业股份有限公司 一种9-卤代甾体激素化合物9-位脱卤的制备方法
EP3882380B1 (fr) * 2020-03-16 2022-04-27 Re:NewCell AB Procédé d'élimination de métal et de blanchiment en une étape ayant lieu en milieu acide
KR102341248B1 (ko) 2020-07-20 2021-12-20 이유진 원격 동반 골프 라운딩 서비스 제공 시스템
CN115093152B (zh) * 2022-06-13 2023-06-16 阳新娲石水泥有限公司 一种复合型降铬助磨剂及其制备方法
CN116289318B (zh) * 2023-04-28 2024-03-26 常州大学 一种纸张脱酸和加固增强的方法

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